High-pressure NMR studies of the water soluble rhodium hydroformylation system

István T. Horváth; Rodney V. Kastrup; Alexis A. Oswald; Edmund J. Mozeleski

doi:10.1007/BF00774589

High-pressure NMR studies of the water soluble rhodium hydroformylation system

István T. Horváth
, Rodney V. Kastrup
, Alexis A. Oswald
, Edmund J. Mozeleski

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

118 Citations (Scopus)

Abstract

Rh(CO)₂(acac) reacts with P(m-C₆H₄SO₃Na.H₂O)₃ (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C₆H₄SO₃Na)₃]₃ (1a), the structure of which is similar to HRh(CO) (PPh₃)₃ (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C₆H₄SO₃Na)₃ does not show the formation of new species up to 200 atm of CO:H₂(1:1). In contrast, 1b, in the presence of three molar excess of PPh₃, is completely converted to HRh(CO)₂(PPh₃)₂ (2b) under 30 atm CO/H₂(1:1) in toluene. The activation energy of the dissociation of P(m-C₆H₄SO₃Na)₃ from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh₃ from 1b in toluene. © 1989 J.C. Baltzer A.G. Scientific Publishing Company.

Original language	English
Pages (from-to)	85-90
Journal	Catalysis Letters
Volume	2
Issue number	2
DOIs	https://doi.org/10.1007/BF00774589
Publication status	Published - Mar 1989
Externally published	Yes

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title = "High-pressure NMR studies of the water soluble rhodium hydroformylation system",

abstract = "Rh(CO)2(acac) reacts with P(m-C6H4SO3Na.H2O)3 (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C6H4SO3Na)3]3 (1a), the structure of which is similar to HRh(CO) (PPh3)3 (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C6H4SO3Na)3 does not show the formation of new species up to 200 atm of CO:H2(1:1). In contrast, 1b, in the presence of three molar excess of PPh3, is completely converted to HRh(CO)2(PPh3)2 (2b) under 30 atm CO/H2(1:1) in toluene. The activation energy of the dissociation of P(m-C6H4SO3Na)3 from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh3 from 1b in toluene. {\textcopyright} 1989 J.C. Baltzer A.G. Scientific Publishing Company.",

author = "Horv{\'a}th, \{Istv{\'a}n T.\} and Kastrup, \{Rodney V.\} and Oswald, \{Alexis A.\} and Mozeleski, \{Edmund J.\}",

year = "1989",

month = mar,

doi = "10.1007/BF00774589",

language = "English",

volume = "2",

pages = "85--90",

journal = "Catalysis Letters",

issn = "1011-372X",

publisher = "Kluwer Academic Publishers",

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TY - JOUR

T1 - High-pressure NMR studies of the water soluble rhodium hydroformylation system

AU - Horváth, István T.

AU - Kastrup, Rodney V.

AU - Oswald, Alexis A.

AU - Mozeleski, Edmund J.

PY - 1989/3

Y1 - 1989/3

N2 - Rh(CO)2(acac) reacts with P(m-C6H4SO3Na.H2O)3 (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C6H4SO3Na)3]3 (1a), the structure of which is similar to HRh(CO) (PPh3)3 (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C6H4SO3Na)3 does not show the formation of new species up to 200 atm of CO:H2(1:1). In contrast, 1b, in the presence of three molar excess of PPh3, is completely converted to HRh(CO)2(PPh3)2 (2b) under 30 atm CO/H2(1:1) in toluene. The activation energy of the dissociation of P(m-C6H4SO3Na)3 from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh3 from 1b in toluene. © 1989 J.C. Baltzer A.G. Scientific Publishing Company.

AB - Rh(CO)2(acac) reacts with P(m-C6H4SO3Na.H2O)3 (P/Rh > 3.5) in water under CO to give HRh(CO)[P(m-C6H4SO3Na)3]3 (1a), the structure of which is similar to HRh(CO) (PPh3)3 (1b). High pressure NMR spectra of an aqueous solution containing 1a and three molar excess of P(m-C6H4SO3Na)3 does not show the formation of new species up to 200 atm of CO:H2(1:1). In contrast, 1b, in the presence of three molar excess of PPh3, is completely converted to HRh(CO)2(PPh3)2 (2b) under 30 atm CO/H2(1:1) in toluene. The activation energy of the dissociation of P(m-C6H4SO3Na)3 from 1a in water was found to be 30±1 kcal/mol, which is 11±1 kcal/mol higher than the dissociation of PPh3 from 1b in toluene. © 1989 J.C. Baltzer A.G. Scientific Publishing Company.

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U2 - 10.1007/BF00774589

DO - 10.1007/BF00774589

M3 - RGC 21 - Publication in refereed journal

SN - 1011-372X

VL - 2

SP - 85

EP - 90

JO - Catalysis Letters

JF - Catalysis Letters

IS - 2

ER -

High-pressure NMR studies of the water soluble rhodium hydroformylation system

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